Photo-labile pro-fragrance conjugates

ABSTRACT

The present invention relates to photo-labile pro-fragrance conjugates comprising:  
     a) a photo-labile unit which upon exposure to electromagnetic radiation is capable of releasing a pro-fragrance unit; and  
     b) a pro-fragrance unit, which when so released is either  
     i) a pro-fragrance compound capable of releasing a fragrance raw material; or  
     ii) a fragrance raw material.  
     The present invention relates to systems for delivering fragrances to a situs, and to laundry detergent compositions, fine fragrances, personal care and hair care compositions comprising said systems.

FIELD OF THE INVENTION

[0001] The present invention relates to photo-labile pro-fragranceconjugates, which are capable of releasing a fragrance raw material in asequence of chemical reaction steps that include a photo-activatedrelease of a nitrogen-containing pro-fragrance compound. The conjugatesare useful in formulating fragrance delivery systems. The conjugates ofthe present invention are capable of delivering any type of fragranceraw material.

BACKGROUND OF THE INVENTION

[0002] Pro-fragrances and pro-accords have been used to enhance thedelivery of fragrance raw materials and to sustain their duration.Typically pro-fragrances and pro-accords deliver alcohol, ketone,aldehyde, and ester fragrance raw materials via substrates which arehydrolyzed by one or more mechanisms, inter alia, the acidic pH of skin,nascent moisture.

[0003] Fragrances or odors not only provide a pleasant aestheticbenefit, but also serve as a signal. For example, foods, which havesoured or are no longer edible, may develop smells, which are repulsiveand send a signal that they are no longer palatable. Therefore, thedelivery of an aroma sensory signal is also a benefit, which apro-fragrance can provide.

[0004] However, pro-fragrances and pro-accords typically rely on thebreak down of a chemical species not based on accidental circumstancebut on deliberate execution. There are currently no fragrance or odorreleasing compounds which involve release of fragrances by way of acontrolled chemical cascade initiated by exposure to electromagneticradiation, inter alia, UV light. The present invention provides a meansfor delivering a fragrance or an accord wherein the delivery of saidfragrance or said accord is instigated by exposure to light.

SUMMARY OF THE INVENTION

[0005] The present invention meets the aforementioned need in that ithas been surprisingly discovered that fragrance raw materials can bedelivered by photo-labile pro-fragrance conjugates. The photo-labilepro-fragrance conjugates of the present invention are activated by theexposure of the conjugates to electromagnetic radiation, which is theinitial step in a chemical cascade resulting in the ultimate release ofa fragrance raw material. One of the steps in the cascade involvesphotochemically initiated fragmentation of a chemical bond between aphoto-labile unit and a nitrogen atom contained within a pro-fragranceunit.

[0006] The conjugates of the present invention comprise:

[0007] a) a photo-labile unit which upon exposure to electromagneticradiation is capable of releasing a pro-fragrance unit; and

[0008] b) a pro-fragrance unit, which when so released is either

[0009] i) a pro-fragrance compound capable of releasing a fragrance rawmaterial; or

[0010] ii) a fragrance raw material.

[0011] The present invention also relates to a photo-labile fragranceconjugate delivery system comprising:

[0012] A) from about 0.001% by weight, of a photo-labile pro-fragranceconjugate, said conjugate comprising:

[0013] a) a photo-labile unit which upon exposure to electromagneticradiation is capable of releasing a pro-fragrance unit;

[0014] b) a pro-fragrance unit, which when so released is either

[0015] i) a pro-fragrance compound capable of releasing a fragrance rawmaterial; or

[0016] ii) a fragrance raw material; and

[0017] B) the balance carriers and adjunct ingredients.

[0018] These and other objects, features, and advantages will becomeapparent to those of ordinary skill in the art from a reading of thefollowing detailed description and the appended claims. All percentages,ratios and proportions herein are by weight, unless otherwise specified.All temperatures are in degrees Celsius (° C.) unless otherwisespecified. All documents cited are in relevant part, incorporated hereinby reference.

DETAILED DESCRIPTION OF THE INVENTION

[0019] The present invention relates to photo-labile pro-fragranceconjugates, which are stable until activated by exposure toelectromagnetic radiation. The conjugates of the present invention arecapable of releasing any type of perfume raw material, inter alia,alcohols, ketones, aldehydes, via a single- or multi-step process thatis initiated by the photo-induced fragmentation of a chemical bondbetween the photo-labile unit and a nitrogen atom in the pro-fragranceunit.

[0020] The conjugates of the present invention can be depicted ascompounds having a photo-labile unit and a pro-fragrance unit which areconnected to one another directly or optionally by way of a linkingunit. The conjugates can be represented by the formula:

[photo-labile unit]-(L)_(n)-[pro-fragrance unit]

[0021] wherein the linking unit, L, is present when the index n is equalto 1 and absent when n is equal to 0.

[0022] For the purposes of the present invention the term “photo-labileunit” is defined herein as “a unit which upon exposure toelectromagnetic radiation becomes the photo-fragment compound byfragmenting from the parent photo-labile pro-fragrance conjugate.” Insome embodiments of the present invention it may be advantageous thatthe photo-fragment compound does not interfere with the aestheticquality or character of the released fragrance or pro-fragrancecompound. In the presence of light, the photo-labile unit serves totrigger the chemical reaction or reaction cascade that ends with theultimate release of one or more fragrance raw materials.

[0023] For the purposes of the present invention the term “pro-fragranceunit” is defined herein as “that portion of the photo-labilepro-fragrance conjugate, which gives rise to the fragrance compound orpro-fragrance compound as a result of exposure of the photo-labilepro-fragrance conjugate to electromagnetic radiation or “light.”

[0024] For the purpose of the present invention the term “pro-fragrancecompound” is defined herein as “a chemical species, which by undergoingone or more chemical transformations results in the release of one ormore fragrance compounds.” Fragrance compounds and fragrance rawmaterials are terms which refer to the final “perfume” ingredients whichare delivered and are used interchangeably herein. What is meant hereinby the term “chemical transformation” includes conversion to a speciesof different molecular formula by any means, inter alia, hydrolysis,photolysis, thermolysis, autoxidation, addition, elimination andsubstitution reactions, as well as conversion to a species with the samemolecular formula, but having an altered chemical orientation, i.e.,isomerized.

[0025] The chemical cascade, which begins the release of a fragrance rawmaterial, may be controlled by requiring a certain wavelength ofelectromagnetic radiation to be present to initiate the releasesequence. For example, “outside light”, which typically comprises thefull range of UV light, may be required to initiate the release of thefragrance precursor. In some cases, high temperatures may also initiatethe chemical cascade.

[0026] Photo-labile Pro-fragrance Conjugates

[0027] The present invention relates to conjugates, which upon exposureto visible light or other forms of electromagnetic radiation, interalia, UV light, releases a fragrance raw material after a series ofchemical transformations, wherein said series involves at least twodiscrete steps. The photo-labile pro-fragrance conjugates of the presentinvention comprise:

[0028] a) a photo-labile unit, which upon exposure to electromagneticradiation is capable of releasing a pro-fragrance unit; and

[0029] b) a pro-fragrance unit, which when so released is either

[0030] i) a pro-fragrance compound capable of releasing a fragrance rawmaterial; or

[0031] ii) a fragrance raw material.

[0032] The conjugates of the present invention comprise a chemicalspecies having a photo-activated unit which is bonded to the nitrogenatom of a pro-fragrance compound, a fragrance raw material, or a linkingunit which is subsequently bonded to the nitrogen atom of apro-fragrance compound, or a fragrance raw material, wherein saidchemical bond is capable of being broken when said conjugate is exposedto electromagnetic radiation.

[0033] For the purposes of the present invention the term “hydrocarbyl”is defined herein as “any unit which comprises carbon and hydrogenatoms, whether linear, branched, cyclic, and regardless of how many ofthe hydrogen atoms are substituted for with a suitable “substituted”unit as defined herein below.” Non-limiting examples of “hydrocarbyl”units include methyl, benzyl, 6-hydroxyoctanyl, m-chlorophenyl,2-(N-methylamino)propyl, and the like.

[0034] The terms “unit which can substitute for hydrogen” and“substituted” are used throughout the specification and for the purposesof the present invention these terms are defined as “chemical moietieswhich can replace a hydrogen atom on a hydrocarbon chain, an aryl ring,and the like, or replacement of a hydrogen atom, two hydrogen atoms, orthree hydrogen atoms from a carbon atom to form a moiety, or thereplacement of hydrogen atoms from adjacent carbon atoms to form amoiety.” For example, a substituted unit that requires a single hydrogenatom replacement includes halogen, hydroxyl, and the like. Atwo-hydrogen atom replacement includes carbonyl, oximino, and the like.Three hydrogen replacement includes cyano, and the like. The termsubstituted is used throughout the present specification to indicatethat a moiety, inter alia, aromatic ring, alkyl chain, can have one ormore of the hydrogen atoms replaced by a substituent. For example,4-hydroxyphenyl is a “substituted aromatic carbocyclic ring”, and3-guanidinopropyl is a “substituted C₃ alkyl unit.”

[0035] The following are non-limiting examples of moieties, which canreplace hydrogen atoms on carbon to form a “substituted hydrocarbyl”unit:

[0036] i) —NHCOR³⁰;

[0037] ii) —COR³⁰;

[0038] iii) —COOR³⁰;

[0039] iv) —COCH=CH₂;

[0040] v) —C(=NH)NH₂;

[0041] vi) —N(R³⁰)₂;

[0042] vii) —NHC₆H₅;

[0043] viii) =CHC₆H₅;

[0044] ix) —CON(R³⁰)₂;

[0045] x) —CONHNH₂;

[0046] xi) —NHCN;

[0047] xii) —OCN;

[0048] xiii) —CN;

[0049] xiv) F, Cl, Br, I, and mixtures thereof;

[0050] xv) =O;

[0051] xvi) —OR³⁰;

[0052] xvii) —NHCHO;

[0053] xviii) —OH;

[0054] xix) —NHN(R³⁰)₂;

[0055] xx) =NR³⁰;

[0056] xxi) =NOR³⁰;

[0057] xxii) —NHOR³⁰;

[0058] xxiii) —CNO;

[0059] xxiv) —NCS;

[0060] xxv) =C(R³⁰)₂;

[0061] xxvi) —SO₃M;

[0062] xxvii) —OSO₃M;

[0063] xxviii) —SCN;

[0064] xxix) —P(O)H₂;

[0065] xxx) —PO₂;

[0066] xxxi) —P(O)(OH)₂;

[0067] xxxii) —SO₂NH₂;

[0068] xxxiii) —SO₂R³⁰;

[0069] xxxiv) —NO₂;

[0070] xxxv) —CF₃, —CCl₃, —CBr₃;

[0071] xxxvi) and mixtures thereof;

[0072] wherein R³⁰ is hydrogen, C₁-C₂₀ linear or branched alkyl, C₆-C₂₀aryl, C₇-C₂₀ alkylenearyl, and mixtures thereof; M is hydrogen, or asalt forming cation. Suitable salt forming cations include, sodium,lithium, potassium, calcium, magnesium, ammonium, and the like.Non-limiting examples of an alkylenearyl unit include benzyl,2-phenylethyl, 3-phenylpropyl, 2-phenylpropyl.

[0073] Photo-labile Units

[0074] The photo-labile units of the present invention may be anymoiety, which is capable of instigating the release of a fragrance rawmaterial by breaking the chemical bond between the photo-labile unit andone of three components:

[0075] a) a fragrance raw material unit thereby directly releasing afragrance raw material;

[0076] b) a pro-fragrance unit thereby instigating a sequence of one ormore chemical transformations which release a fragrance raw material; or

[0077] c) a linking group which further undergoes a sequence of one ormore chemical transformations which subsequently release a fragrance rawmaterial or pro-fragrance unit.

[0078] A first aspect of photo-labile units according to the presentinvention relate to units which are aryl acrylic acid units having theformula:

[0079] wherein R is a fragrance raw material or a unit capable ofreleasing a fragrance raw material; each R¹ is independently hydrogen, aunit which can substitute for hydrogen, C₁-C₁₂ substituted orunsubstituted hydrocarbyl unit, each R² is independently hydrogen,C₁-C₁₂ substituted or unsubstituted hydrocarbyl unit, and mixturesthereof; X is selected from the group consisting of —OH, —OC(O)R¹²,—OC(O)OR¹², —NHR¹², and mixtures thereof; R¹² is H, C₁-C₁₂ substitutedor unsubstituted alkyl, and mixtures thereof. These units are capable ofreleasing a fragrance raw material unit, a pro-fragrance unit, or alinking group bonded fragrance raw material unit or pro-fragrance unit;the photo-fragment compound having the formula:

[0080] which can optionally be a fragrance raw material itself, interalia, coumarin.

[0081] Non-limiting examples of photo-labile units included in thisfirst aspect include a pro-fragrance wherein X is —NH₂, the R¹ unit ishydroxy, and both R² units are hydrogen which relates to3-(2-amino-4-hydroxyphenyl)-acrylamide fragrance raw materials havingthe formula:

[0082] Another example relates to photo-labile units having the formula:

[0083] wherein both R¹ and X are hydroxyl.

[0084] A second aspect of the present invention relates to aphoto-labile pro-fragrance conjugates having the formula:

[0085] wherein R¹ is one or more electron donating groups; non-limitingexamples of which include hydroxy, C₁-C₁₂ linear or branched alkoxy,—N(R¹²)₂, and mixtures thereof; R¹² is H, C₁-C₁₂ alkyl, and mixturesthereof, and the like.

[0086] A third aspect of the photo-labile units relates to aryl unitshaving the formula:

[0087] A fourth aspect of the photo-labile units relates to aryl unitshaving the formula:

[0088] wherein B is a photo-labile unit which reactivity is enhanced ormodulated by the aryl unit which comprises the balance of thephoto-labile component. One embodiment of this aspect relates to siliconatom comprising units having the formula:

[0089] wherein R¹ is the same as defined herein above. Furthernon-limiting examples of embodiments of this aspect of the photo-labileunits include compounds having the formula:

[0090] Linking Units

[0091] Depending upon the structure of the photo-labile unit and therate at which the formulator desires the final fragrance raw material tobe released, the use of an optional linking unit, L, may be desired ornecessary. An example of a compound having an L unit present has theformula:

[0092] one embodiment of which has the formula:

[0093] One aspect of the present invention relates to L units which are—OC(O)—, —NR³C(O)—, —OC(R³R⁴)—, and —C(O)— carbonyl units. However, anysuitable unit which facilitates the breakdown of the releasedpro-fragrance can serve as a linking unit in the photo-activatedpro-fragrance conjugates of the present invention.

[0094] When the pro-fragrance unit is released from the photo-labileunit when a linker unit is present, the release of the photo-fragmentcompound and pro-fragrance or fragrance compound is accompanied by therelease of a linker compound. For example, when the L unit is —OC(O)—,the linker compound is CO2.

[0095] When the L unit is —OC(R³R⁴)— the linker compound released can bean aldehyde or a ketone. In one aspect of the present invention, thealdehyde or ketone released is a perfume raw material.

[0096] Non-limiting examples of photo-activated compounds comprising anL unit include:

[0097] Pro-fragrance Units

[0098] Pro-fragrance units are released from the parent conjugatemolecules when the conjugate is fragmented by a photochemical reaction.The pro-fragrance units of the present invention are attached to thephoto-labile units either directly or by way of an optional linkingunit, L.

[0099] As will be understood by the formulator, not all fragrance rawmaterials can be released from the same form of pro-fragrance. The twoprimary aspects of the present invention as it relates to release of apro-fragrance unit are determined by the type of reaction whichultimately releases the final fragrance raw material.

[0100] The first aspect relates to type A release which involves aretro-Michael reaction, and the second aspect relates to type B releasewhich involves a hydrolysis reaction.

[0101] Type A Release

[0102] The first aspect of the pro-fragrance unit component of thepresent invention relates to the release of fragrance raw materialprecursors which undergo a retro-Michael reaction.

[0103] Without wishing to be limited by theory, the reaction cascadewhich releases the fragrance raw material via retro-Michael reaction isbelieved to proceed according to the general scheme as depicted belowfor the release of a α, β-unsaturated ketone, inter alia, damascone.

[0104] 1. A first photo-isomerization step:

[0105] 2. A second pro-fragrance unit elimination step:

[0106] 3. A third retro-Michael elimination step:

[0107] The pro-fragrances which comprise this aspect of the presentinvention have the formula:

[0108] wherein each R³ is independently hydrogen, substituted orunsubstituted C₁-C₃₀ hydrocarbyl, and mixtures thereof.

[0109] One embodiment of this aspect of the present invention relates topro-fragrances having the formula:

[0110] wherein each R⁴ is independently selected from the groupconsisting of:

[0111] i) hydrogen;

[0112] ii) C₁-C₂₂ substituted or unsubstituted, branched or unbranchedalkyl;

[0113] iii) C₂-C₂₂ substituted or unsubstituted, branched or unbranchedalkenyl;

[0114] iv) C₂-C₂₀ substituted or unsubstituted, branched or unbranchedhydroxyalkyl;

[0115] v) C₇-C₂₀ substituted or unsubstituted alkylenearyl;

[0116] vi) C₃-C₂₀ substituted or unsubstituted cycloalkyl;

[0117] vii) C₆-C₂₀ aryl;

[0118] viii) C₅-C₂₀ heteroaryl units comprising one or more heteroatomsselected from the group consisting of nitrogen, oxygen, sulfur, andmixtures thereof;

[0119] ix) two R⁴ units can be taken together to form one or morearomatic or non-aromatic, heterocyclic or non-heterocyclic, singlerings, fused rings, bicyclo rings, spiroannulated rings, or mixturesthereof, said rings comprising from 3 to 20 carbon atoms and one or moreheteroatoms selected from the group consisting of nitrogen, oxygen,sulfur, and mixtures thereof;

[0120] x) and mixtures thereof; G¹ and G² are each independentlyhydrogen, C₁-C₂₀ linear or branched hydrocarbyl, —Y, —C(O)Y, andmixtures thereof; Y is C₆-C₁₀ substituted or unsubstituted cyclic alkyl.Non-limiting examples of embodiments of Y include2,6,6-trimethylcyclohex-2-enyl, 2,6,6-trimethylcyclohex-1-enyl,2,6,6-trimethylcyclohex-1-enyl, 2,6,6-trimethylcyclohex-3-enyl, and thelike.

[0121] Another embodiment of this aspect of the present inventionrelates to pro-fragrances having the formula:

[0122] wherein G¹ and G² are each independently —CH₃, —C(O)CH₃, —Y,—C(O)Y, and mixtures thereof; Y is selected from the group consistingof:

[0123] i) 2,6,6-trimethylcyclohex-2-enyl having the formula:

[0124] ii) 2,6,6-trimethylcyclohex-1-enyl having the formula:

[0125] iii) 2,6,6-trimethylcyclohex-1-enyl having the formula:

[0126] iv) 2,6,6-trimethylcyclohex-3-enyl having the formula:

[0127] v) and mixtures thereof.

[0128] The following is a non-limiting example of a photo-labilepro-fragrance which releases a fragrance raw material (6-damascone) viaretro-Michael elimination.

[0129] The following is a non-limiting example of a photo-labilepro-fragrance which comprises a linking unit and which releases afragrance raw material (δ-damascone) via retro-Michael reaction.

[0130] However, R³ units in another aspect of the present invention canbe taken together with an R¹ or R² unit of the photo-labile unit or withan L unit to form a C₂-C₆ heterocyclic ring for example, the conjugatehaving the formula:

[0131] which is capable of releasing damascone and a photo-fragmentcompound having the proposed formula:

[0132] Type B Release

[0133] The second aspect of the pro-fragrance unit component of thepresent invention relates to the release of fragrance raw materialprecursors which undergo a hydrolysis step in the cascade releasing thefragrance raw material.

[0134] Without wishing to be limited by theory, the reaction cascadewhich releases the fragrance raw material via hydrolysis reaction isbelieved to proceed according to the general scheme as depicted belowfor the release of an aldehyde, inter alia, citral.

[0135] 1. A first photo-isomerization step:

[0136] 2. A second pro-fragrance unit elimination step:

[0137] 3. A third hydrolysis step:

[0138] However, the above scheme only illustrates the general case ofpro-fragrances which are in the form of oxazolidinones or oxazineshaving the formula:

[0139] each of which is capable of releasing an aldehyde having theformula R⁵CHO.

[0140] However, the heterocyclic ring embodiment which comprises thepro-fragrance units of the present invention which have the generalformula:

[0141] wherein Z is oxygen or sulfur; in one embodiment comprisingoxazolidines, Y is oxygen and the index m is 1.

[0142] R⁵ and R⁶ units are selected such that upon hydrolysis of thepro-fragrance compound, aldehyde or ketone fragrance raw materials arereleased. When an aldehyde is released R⁶ is hydrogen.

[0143] As stated herein above, R⁵ units can be any substituted orunsubstituted hydrocarbyl unit, non-limiting examples of which includeR⁵ units which comprise:

[0144] a) C₆-C₂₂ substituted or unsubstituted linear alkyl; C₆-C₁₂ alkylwhen aliphatic aldehydes are released, inter alia, hexanal, octanal,nonanal, decanal, undecanal, and dodecanal;

[0145] b) C₆-C₂₂ substituted or unsubstituted branched alkyl;2-methyidecanal, 2-methylundecanal;

[0146] c) C₆-C₂₂ substituted or unsubstituted linear alkenyl; C₆-C₁₂alkenyl when unsaturated linear aldehydes are released, inter alia,trans-4-hexenal, cis-4-heptenal, and 10-undecenal;

[0147] d) C₆-C₂₂ substituted or unsubstituted branched alkenyl; C₉ orC₁₄ branched alkyl when the released aldehyde is a terpene orsesquiterpene aldehyde, inter alia, citronellal, citral;

[0148] e) C₆-C₂₂ substituted or unsubstituted cycloalkyl; C₉ or C₁₁alkyl substituted cycloalkyl when the released ketone is cyclicterpenoid, inter alia, α, β, γ, and δ ionone or damascone;

[0149] f) C₆-C₂₂ substituted or unsubstituted branched cycloalkyl;

[0150] g) C₆-C₂₂ substituted or unsubstituted cycloalkenyl;

[0151] h) C₆-C₂₂ substituted or unsubstituted branched cycloalkenyl;

[0152] i) C₆-C₂₂ substituted or unsubstituted aryl;

[0153] h) C₆-C₂₂ substituted or unsubstituted heterocyclicalkyl;

[0154] k) C₆-C₂₂ substituted or unsubstituted heterocyclicalkenyl;

[0155] l) and mixtures thereof; R⁶ units comprise:

[0156] a) hydrogen;

[0157] b) C₁-C₁₀ substituted or unsubstituted linear alkyl; as in thecase of methyl ketones, interalia, α, β, γ, and δ ionone;

[0158] c) C₃-C₁₀ substituted or unsubstituted branched alkyl; forexample, tagetone wherein R is 2-methyl-1,3-dieneyl and R¹ is isobutyl;

[0159] d) C₂-C₁₀ substituted or unsubstituted linear alkenyl; as in thecase of α, β, γ, and δ damascone;

[0160] e) C₃-C₁₀ substituted or unsubstituted branched alkenyl;

[0161] f) C₃-C₁₅ substituted or unsubstituted cycloalkyl;

[0162] g) C₄-C₁₅ substituted or unsubstituted branched cycloalkyl;

[0163] h) C₄-C₁₅ substituted or unsubstituted cycloalkenyl;

[0164] i) C₅-C₁₅ substituted or unsubstituted branched cycloalkenyl;

[0165] j) C₆-C₁₅ substituted or unsubstituted aryl;

[0166] k) C₆-C₂₂ substituted or unsubstituted heterocyclicalkyl;

[0167] l) C₆-C₂₂ substituted or unsubstituted heterocyclicalkenyl;

[0168] m) and mixtures thereof; alternatively the R⁵ and R⁶ units can betaken together to form a substituted or unsubstituted ring having in thering from 3 to 10 carbon atoms; for example, R5 and R⁶ taken togethercan be fused ring comprising ketones, inter alia, nootkatone; ormono-cyclic ketones, inter alia, menthone, isomenthone, carvone, andfenchone.

[0169] For the hydrolyzable ring pro-fragrances of the present inventioneach R⁷ is independently selected from any substituted or unsubstitutedhydrocarbyl unit, non-limiting embodiments are selected from the groupconsisting of:

[0170] a) R⁶;

[0171] b) hydroxyl;

[0172] c) a carbonyl comprising unit having the formula:

—(CH₂)_(x)COR⁸

[0173] wherein R⁸ is:

[0174] i) —OH;

[0175] ii) —OR⁹ wherein R⁹ is hydrogen, C₁-C₁₅ substituted linear alkyl,C₁₁-C₁₅ unsubstituted linear alkyl, C₁-C₁₅ substituted branched alkyl,C₁₁-C₁₅ unsubstituted branched alkyl, C₂-C₂₂ substituted orunsubstituted linear alkenyl, C₃-C₂₂ substituted or unsubstitutedbranched alkenyl, or mixtures thereof, wherein said substitution is nothalogen or thioalkyl; R⁹ is methyl, R⁹ is hydrogen and Z is oxygen orsulfur when an oxazolidine is formed from the methyl esters of serine,threonine, cysteine, and the like;

[0176] iii) —N(R¹⁰)₂ wherein R¹⁰ is hydrogen, C₁-C₆ substituted orunsubstituted linear alkyl, C₃-C₆ substituted or unsubstituted branchedalkyl, or mixtures thereof;

[0177] iv) C₁-C₂₂ substituted or unsubstituted linear alkyl;

[0178] v) C₁-C₂₂ substituted or unsubstituted branched alkyl;

[0179] vi) C₂-C₂₂ substituted or unsubstituted linear alkenyl;

[0180] vii) C₃-C₂₂ substituted or unsubstituted branched alkenyl;

[0181] viii) C₃-C₂₂ substituted or unsubstituted cycloalkyl;

[0182] ix) C₆-C₂₂ substituted or unsubstituted aryl;

[0183] x) C₆-C₂₂ substituted or unsubstituted heterocyclicalkyl;

[0184] xi) C₆-C₂₂ substituted or unsubstituted heterocyclicalkenyl; theindex x is from 0 to 22;

[0185] d) alkyleneoxy units having the formula:

—[C(R¹¹)₂]_(y)[C(R¹¹)₂O]_(z)R¹¹

[0186] wherein each R¹¹ is independently;

[0187] i) hydrogen;

[0188] ii) —OH;

[0189] iii) C₁-C₄ alkyl;

[0190] iv) or mixtures thereof; two R¹¹ units can be taken together toform a C₃-C₆ spiroannulated ring, carbonyl unit, or mixtures thereof; yhas the value from 0 to 10, z has the value from 1 to 50;

[0191] e) and mixtures thereof; any two R⁷ units can be taken togetherto form:

[0192] i) a carbonyl moiety;

[0193] ii) a C₃-C₆ spiroannulated ring;

[0194] iii) a heterocyclic aromatic ring comprising from 5 to 7 atoms;

[0195] iv) a non-heterocyclic aromatic ring comprising from 5 to 7atoms;

[0196] v) a heterocyclic ring comprising from 5 to 7 atoms;

[0197] vi) a non-heterocyclic ring comprising from 5 to 7 atoms;

[0198] vii) or mixtures thereof; and the index m is an integer from 1 to3.

[0199] For example, each of the ring carbon atoms may have one or bothof the hydrogen atoms substituted as defined herein above or takentogether to form an aromatic or non-aromatic, carbocyclic orheterocyclic ring, for example:

[0200] One iteration of this embodiment relates to oxazolidines havingthe formula:

[0201] wherein R⁶ is selected from the group consisting of hydrogen andmethyl; each R⁷ is independently hydrogen, methyl, —C(O)OR⁹ and mixturesthereof; R⁹ is hydrogen, C₁-C₁₂ alkyl, and mixtures thereof.

[0202] The following is a non-limiting example of the oxazolidoneembodiment of the present invention.

[0203] Hydrolysis based release of the fragrance raw material canproceed by way of any hydrolyzable pro-fragrance compound which isinitiated by the release of the pro-fragrance unit from a photo-labilepro-fragrance conjugate. For example, the ionone series of ketonefragrance raw materials, unlike the damascone series delivered by Type ARelease, are formed into photo-labile pro-fragrance conjugates in whichthe photo-labile unit is connected to a pro-fragrance unit consisting ofa pro-fragrance compound that is an imine or an enamine that arethemselves formed from the reaction of an aldehyde or ketone fragranceraw material with an amine compound. The imine- or iminium-basedpro-fragrance compounds are released upon activation of the conjugate.The following is an example of a photo-labile pro-fragrance conjugatethat is capable of releasing an enamine-based pro-fragrance compound ofthe present invention.

[0204] The Type B Release photo-activated pro-fragrances can alsocomprise a suitable linking group for example a compound having theformula:

[0205] Another type of Type B Release relates to aminals or ketalshaving, for example, the formula:

[0206] which is capable of releasing an aldehyde or ketone fragrance rawmaterial having the formula R⁵CHO or R⁵R⁶CHO and an alcohol having theformula R′OH. R′OH can be a fragrance raw material or not a fragranceraw material depending on the needs of the formulator. A non-limitingexample of an aminal according to the present invention has the formula:

[0207] The formulator when using aminals to deliver two fragrance rawmaterials can make use of the R³ nitrogen unit to control the releaserate of the fragrance raw materials once the photo-labile unit hasreleased the pro-fragrance component. The formulator can make use of theR³ nitrogen unit to control the physical properties of the photo-labilepro-fragrance conjugate. Such properties include, but are not limitedto, the ability of the conjugate to deposit on a desired surface in anaqueous wash environment.

[0208] A further example of Type B Release relates to conjugates whichare activated by the breaking of the bond between the photo-labile unitand the pro-fragrance unit, wherein an intramolecular reaction ensueswhich displaces a pro-fragrance compound which then hydrolyzes torelease the fragrance raw material. A non-limiting general example isthe amino-amide photo-labile pro-fragrance conjugate depicted in thescheme below:

[0209] 1. A photo-isomerization followed by a pro-fragrance compoundelimination step:

[0210] 2. A subsequent cyclization step:

[0211] 3. A final elimination step:

[0212] Fragrance Raw Materials

[0213] Mixtures of fragrance materials are known by those skilled in theart of fragrances and perfumes as “accords”. The term “accord” as usedherein is defined as “a mixture of two or more ‘fragrance raw materials’which are artfully combined to impart a pleasurable scent, odor,essence, or fragrance characteristic”. For the purposes of the presentinvention “fragrance raw materials” are herein defined as compoundshaving a molecular weight of at least 100 g/mol and which are useful inimparting an odor, fragrance, essence, or scent either alone or incombination with other “fragrance raw materials”. For the purposes ofthe present invention, fragrance raw materials which comprise an aminounit can be directly attached to the photo-labile unit and, therefore,released directly without further reaction.

[0214] Typically “fragrance raw materials” comprise inter alia alcohols,ketones, aldehydes, esters, ethers, nitriles, and alkenes such asterpenes. A listing of common “fragrance raw materials” can be found invarious reference sources, for example, “Perfume and Flavor Chemicals”,Vols. I and II; Steffen Arctander Allured Pub. Co. (1994) and “Perfumes:Art, Science and Technology”; Müller, P. M. and Lamparsky, D., BlackieAcademic and Professional (1994) both incorporated herein by reference.

[0215] Examples of fragrance raw material ketones which are capable ofbeing released by the compounds of the present invention include1-(2,6,6-trimethylcyclohex-2-enyl)-2-butene-1-one (α-damascone),1-(2,6,6-trimethyl-cyclohex-1-enyl)-2-butene-1-one (β-damascone),1-(2-methylene-6,6-dimethyl-cyclohexanyl)-2-butene-1-one (γ-damascone),1-(2,6,6-trimethylcyclohex-3-enyl)-2-butene-1-one (δ-damascone),4-(2,6,6-trimethylcyclohex-2-enyl)-3-butene-2-one (β-ionone),4-(2,6,6-trimethylcyclohex-1-enyl)-3-butene-2-one (β-ionone),4-(2-methylene-6,6-dimethylcyclo-hexanyl)-3-butene-2-one (γ-ionone).

[0216] Aldehydes which are releasable from the photo-activatedconjugates of the present invention include but are not limited tophenylacetaldehyde, p-methyl phenylacetaldehyde, p-isopropylphenylacetaldehyde, methyinonyl acetaldehyde, phenylpropanal,3-(4-t-butylphenyl)-2-methyl propanal, 3-(4-t-butylphenyl)-propanal,3-(4-methoxyphenyl)-2-methylpropanal,3-(4-isopropylphenyl)-2-methylpropanal,3-(3,4-methylenedioxyphenyl)-2-methylpropanal,3-(4-ethylpheny)-2,2-dimethylpropanal, phenylbutanal,3-methyl-5-phenylpentanal, hexanal, trans-2-hexenal, cis-hex-3-enal,heptanal, cis-4-heptenal, 2-ethyl-2-heptenal, 2,6-dimethyl-5-heptenal,2,4-heptadienal, octanal, 2-octenal, 3,7-dimethyloctanal,3,7-dimethyl-2,6-octadien-1-al, 3,7-dimethyl-1,6-octadien-3-al,3,7-dimethyl-6-octenal, 3,7-dimethyl-7-hydroxyoctan-1 -al, nonanal,6-nonenal, 2,4-nonadienal, 2,6-nonadienal, decanal, 2-methyl decanal,4-decenal, 9-decenal, 2,4-decadienal, undecanal, 2-methyidecanal,2-methylundecanal, 2,6,10-trimethyl-9-undecenal, undec-10-enyl aldehyde,undec-8-enanal, dodecanal, tridecanal, tetradecanal, anisaldehyde,bourgenonal, cinnamic aldehyde, α-amylcinnam-aldehyde, α-hexylcinnamaldehyde, methoxy-cinnamaldehyde, citronellal,hydroxy-citronellal, isocyclocitral, citronellyl oxyacet-aldehyde,cortexaldehyde, cumminic aldehyde, cyclamen aldehyde, florhydral,heliotropin, hydrotropic aldehyde, lilial, vanillin, ethyl vanillin,benzaldehyde, p-methyl benzaldehyde, 3,4-dimethoxybenzaldehyde, 3- and4-(4-hydroxy-4-methyl-pentyl)-3-cyclohexene-1-carboxaldehyde,2,4-dimethyl-3-cyclohexene-1-carboxaldehyde,1-methyl-3-(4-methylpentyl)-3-cyclohexencarboxaldehyde,p-methylphenoxyacetaldehyde, and mixtures thereof.

[0217] Fragrance raw materials suitable for use in the present inventionare described in U.S. Pat. No. 5,919,752 Morelli et al., issued Jul. 6,1999; U.S. Pat. No. 6,013,618 Morelli et al., issued Jan. 11, 2000; U.S.Pat. No. 6,077,821 Morelli et al., issued Jun. 20, 2000; U.S. Pat. No.6,087,322 Morelli et al., issued Jul. 11, 2000; U.S. Pat. No. 6,114,302Morelli et al., issued Sep. 5, 2000; U.S. Pat. No. 6,177,389 Morelli etal., issued Jan. 23, 2001; all of which are incorporated herein byreference.

[0218] Odor Detection Threshold

[0219] For the purposes of the present invention the term “odordetection threshold”is defined as the level at which a fragrance rawmaterial is perceptible to the average human. The odor detectionthreshold (ODT) of the compositions of the present invention arepreferably measured by carefully controlled gas chromatograph (GC)conditions as described hereinbelow.

[0220] Determination of Odor Detection Thresholds is as follows. A gaschromatograph is characterized to determine the exact volume of materialinjected by a syringe, the precise split ratio, and the hydrocarbonresponse using a hydrocarbon standard of known concentration andchain-length distribution. The airflow rate in accurately measured and,assuming the duration of a human inhalation to last 0.02 minutes, thesampled volume is calculated. Since the precise concentration at thedetector at any point in time is known, the mass per volume inhaled isknown and hence the concentration of material. To determine whether amaterial has a threshold below 1 0 ppb, solutions are delivered to thesniff port at the back-calculated concentration. A panelist sniffs theGC effluent and identifies the retention time when odor is notice. Theaverage over all panelists determines the threshold of noticeability orODT. The necessary amount of analyte is injected onto the column toachieve a 10 ppb concentration at the detector. Typical gaschromatograph parameters for determining odor detection thresholds arelisted below. GC: 5890 Series II with FID detector 7673 Auto samplerColumn: J&W Scientific DB-1, length 30 m, i.d. 0.25 mm, film thickness 1

m. Split Injection: 17/1 split ratio Autosampler: 1.13

l/injection Column flow: 1.10 mL/min Air flow: 345 mL/min Inlettemperature: 245° C. Detector temperature: 285° C. TemperatureInformation:

[0221] Initial temperature: 50° C.

[0222] Rate: 5° C./min

[0223] Final temperature: 280° C.

[0224] Final time: 6 min Leading assumptions: 0.02 minutes per sniff andthat GC air adds to sample dilution.

[0225] A general first procedure relates to the conversion of a startingmaterial having formula 1 to the aryl acrylamide photo-labilepro-fragrance 3 by way of the intermediate aryl acrylic acid 2 asdepicted in the following scheme:

[0226] In the case wherein X is equal to oxygen (coumarin derivatives)the preparation begins with a von Pechmann condensation as in theexample of the reaction of resorcinol with acetoacetic acid ethyl esterdepicted in the following scheme:

[0227] Coumarin syntheses are reviewed by Dean, F. M. “NaturallyOccurring Oxygen Ring Compounds”; Butterworths: London, 1963; p. 176.

[0228] Preparation of 3-(2,4-dihydroxy-phenyl)-acrylic acid (5) from7-hydroxy-chromen-2-one (4):

[0229] To a solution of 20% sodium sulfite (640 g) at 60° C. is added7-hydroxy-chromen-2-one (75.0 g, 0.416 mol). The reaction mixture iswarmed to 100° C. and stirred for 1.5 h. To this solution is addeddropwise 30% KOH solution (301 g). The stirred mixture is cooled to 0°C. and acidified by the slow and careful addition of concentrated HCl,keeping the solution temperature below 10° C. The colorless precipitateis separated by filtration, washed with water and dried for 12 h undervacuum at 45° C. The resulting 3-(2,4-dihydroxy-phenyl)-acrylic acid isa colorless solid (24.0 g) and is used without further purification.

EXAMPLE 1

[0230] Preparation of triplal oxazolidine coniugate (7)

[0231] Step (1) preparation of2-(2,4-Dimethyl-cyclohex-3-enyl)-oxazolidine (6):

[0232] To a 0° C. stirred solution of 66 g (0.47 mol) triplal and 21 gsodium sulfate in 150 mL of methanol is added 29 g (0.47 mol) ofethanolamine. The reaction is allowed to warm to room temperature. Afterstirring for 24 h the mixture is cooled to 0° C. and the solids areremoved via vacuum filtration through Celite. Evaporation of the solventgives a clear, slightly yellow oil.

[0233] Step (2) preparation of1-[2-(2,4-Dimethyl-cyclohex-3-enyl)-oxazolidin-3-yl]-3-(2-hydroxy-phenyl)-propenone(7):

[0234] To a 0° C. solution of 8.2 g (0.050 mol) ofo-hydroxy-trans-cinnamic acid in 500 mL of anhydrous tetrahydrofuran(THF) is added 10.3 g (0.050 mol) of 1,3-dicyclohexylcarbodiimide (DCC).After stirring for 10 min, 6.8 g (0.050 mol) of 1-hydroxybenzotriazole(HOBt), 8.2 g (0.045 mol) of2-(2,4-dimethyl-3-cyclohexen-1-yl)-1,3-oxazolidine and 1.1 g (0.009 mol)of 4-(dimethylamino)pyridine (DMAP) is added and stirred at 0° C. for 1h, warmed to room temperature and stirred for an additional 24 h. Themixture is cooled to 0° C., filtered and the solvent is removed invacuo. The residue is diluted with ethyl acetate and washed three timeswith saturated sodium bicarbonate, followed by 10% citric acid andbrine. The organic layer is dried over anhydrous magnesium sulfate,filtered and concentrated in vacuo. The product 7 is further purified byflash chromatography on basic alumina with 20:1 chloroform methanol.

EXAMPLE 2

[0235] Preparation of dihydro-β-ionone oxazine conjugate (9)

[0236] Step (1) preparation of2-Methyl-2-[2-(2,6,6-trimethyl-cyclohex-1-enyl)-ethyl]-[1,3]oxazinane(8):

[0237] To a 0° C. stirred solution of 4-(2,6,6-trimethyl-cyclohex-1-enyl)-butan-2-one (25.2 g, 0.13 mol) and sodium sulfate (20 g) in 80 mLof methanol is added 3-amino-1-propanol (10 g, 0.13 mol). The reactionis allowed to warm to room temperature. After stirring for 24 h themixture is cooled to 0° C. and the solids are removed via vacuumfiltration through Celite. Evaporation of the solvent gives a clearyellow oil.

[0238] Step (2) preparation of3-(2,4-Dihydroxy-phenyl)-1-{2-methyl-2-[2-(2,6,6-trimethyl-cyclohex-1-enyl)-ethyl]-[1,3]oxazinan-3-yl}-but-2-en-1-one (9):

[0239] To a 0° C. solution of 11.1 g (0.050 mol) of3-(2,4-dihydroxy-phenyl)-3-methyl-acrylic acid in 500 mL of anhydrousTHF is added 10.3 g (0.050 mol) of DCC. After stirring for 10 min, 6.8 g(0.050 mol) of HOBt, 11.3 g (0.045 mol) of2-methyl-2-[2-(2,6,6-trimethyl-cyclohex-1 -enyl)-ethyl]-[1,3]oxazinane(8) and 1.1 g (0.009 mol) of DMAP are added and stirred at 0° C. for 1h, warmed to room temperature and stirred for an additional 24 h. Themixture is cooled to 0° C., filtered and the solvent is removed invacuo. The residue is diluted with ethyl acetate and washed three timeswith saturated sodium bicarbonate, followed by 10% citric acid andbrine. The organic layer is dried over anhydrous magnesium sulfate,filtered and concentrated in vacuo. The product 9 is further purified byflash chromatography on basic alumina with 20:1 chloroform/methanol.

EXAMPLE 3

[0240] Preparation of δ-damascone Michael adduct conjugate (11)

[0241] Step (1) Preparation of3-Amino-1-(2,6,6-trimethyl-cyclohex-3-enyl)-butan-1-one (10):

[0242] To a 0° C. stirred solution of 66.2 g (0.574 mol, 1.2 equiv) of1-(2,6,6-trimethyl-cyclohex-3-enyl)-but-2-en-1-one (δ-damascone) in 250mL of ethanol is added 143.3 mL (1 equiv, 0.287 mol) of ammonia(Aldrich, 2.0 M in ethanol). The reaction is allowed to warm to roomtemperature. After stirring for 24 h, the ethanol is concentrated byrotary evaporation to give an oil consisting of 10.

[0243] Step (2) Preparation of 3-(2,4-Dihydroxy-phenyl)-N-[1-methyl-3-oxo-3-(2,6,6-trimethyl-cyclohex-3-enyl)-propyl]-acrylamide(11):

[0244] To a solution of3-amino-1-(2,6,6-trimethyl-cyclohex-3-enyl)-butan-1-one (2.38, 11.3mmol,10) and triethylamine (2.30 g, 22.6 mmol) in anhydrous THF (150 mL)stirred for 5 min at 22° C. is added 3-(2,4-dihydroxyphenyl)-acrylicacid (2.04 g, 11.3 mmol). To this heterogeneous solution is added BOPReagent (5.00 g, 11.3 mmol; Aldrich #22,608-4) in DMF (10 mL), and thesubsequent homogeneous reaction mixture is stirred for 1 h. The reactionmixture is partitioned between ether (200 mL) and water (400 mL); theorganic layer is removed and washed with ether (200 mL). The combinedorganic layers are washed sequentially with saturated sodium bicarbonatesolution (200 mL) and brine (200 mL). The organic layer is dried overanhydrous magnesium sulfate, vacuum filtered and concentrated to give3-(2,4-dihydroxy-phenyl)-acrylic acid 1,5-dimethyl-1-vinyl-hex-4-enylester as an oil that is purified by flash chromatography to give 11 as acolorless solid.

EXAMPLE 4

[0245] Preparation of bis-δ-damascone Michael adduct coniugate (15)

[0246] Step (1) To a 0° C. stirred solution of 96 g (0.50 mol) of1-(2,6,6-trimethyl-cyclohex-3-enyl)-but-2-en-1-one (δ-damascone) in 250mL of ethanol is added 47 g (0.25 mol) ofN¹-[3-(3-Amino-propylamino)-propyl]-propane-1,3-diamine. The reaction isallowed to warm to room temperature. After stirring for 24 h, theethanol is concentrated by rotary evaporation to give3-[3-(3-{3-[1-methyl-3-oxo-3-(2,6,6-trimethyl-cyclohex-3-enyl)-propylamino]-propylamino}-propylamino)-propylamino]-1-(2,6,6-trimethyl-cyclohex-3-enyl)-butan-1-one(bis-Michael adduct 14) as an oil.

[0247] Step (2) which is conversion of starting material 12 tointermediate 13 can be a accomplished by the method described inSynthetic Comm. 1991, 21, 351 included herein by reference.

[0248] Step (3) conversion of intermediate 13 to 15.

[0249] A solution of intermediate 13 (1.2 g, 3.7 mmol), thionyl chloride(2 equiv, 0.88 g, 7.4 mmol, 0.54 mL) in anhydrous toluene (50 mL) isrefluxed for 3 h under an inert atmosphere. The reaction mixture isevaporated to dryness under vacuum and to the crude acid chloride isadded another portion of toluene (50 mL). Bis-Michael adduct 14 (1.1 g,1.9 mmol) is added and the reaction mixture is allowed to stir for 12 h.The mixture is diluted with toluene (100 mL) and washed with 100 mLportions of 1 N HCl, water and brine. The organic layer is dried overanhydrous magnesium sulfate, filtered and concentrated to giveacyl-protected 15. Removal of the acetoxy units by the method ofSynthetic Comm. 1991, 21, 351, incorporated herein by reference, affords15.

Formulations

[0250] The present invention relates to a photo-labile fragrancedelivery system which delivers a photo-labile pro-fragrance conjugate.The pro-fragrance relies upon the photo-initiated cascade to deliver thefragrance raw material. Because it is not necessary that thepro-fragrance compound immediately begins releasing an aldehyde orketone once the photo-labile unit has released said pro-fragrancecompound, the formulator may form a wide array of delivery systems. Ingeneral, the systems of the present invention comprise severalembodiments having various ranges of pro-fragrance conjugate, forexample:

[0251] a) from about 0.001% to about 5%, another embodiment comprisesfrom about 0.005% to about 1%, a range of from about 0.01% to about 0.2%encompasses yet another embodiment, while a further embodiment comprisesfrom about 0.02% to about 0.1% by weight, of a photo-activatedpro-fragrance conjugate, said conjugate comprising:

[0252] i) a photo-labile unit which upon exposure to electromagneticradiation is capable of releasing a pro-fragrance unit as apro-fragrance compound; and

[0253] ii) a pro-fragrance compound, which when so released is capableof releasing a fragrance raw material; and

[0254] Another aspect of the present invention relates to conjugates ofthe present invention that comprise a photo-labile pro-fragranceconjugate comprising a photo-labile unit which upon exposure toelectromagnetic radiation is capable of releasing a pro-fragrance unitas a fragrance compound.

[0255] b) the balance carriers and adjunct ingredients.

[0256] The photo-labile pro-fragrances of the present invention havewide utility in perfumes and fine fragrances. This embodiment of thepresent invention comprises:

[0257] A) from about 0.001% by weight, of one or more photo-activatedpro-fragrance conjugates, said conjugates each comprising:

[0258] a) a photo-labile unit which upon exposure to electromagneticradiation is capable of releasing a pro-fragrance unit;

[0259] b) a pro-fragrance unit, which when so released is either

[0260] i) a pro-fragrance compound capable of releasing a fragrance rawmaterial; or

[0261] ii) a fragrance raw material;

[0262] B) from about 0.01% to about 99% by weight, of an admixture offragrance raw material; and

[0263] C) the balance carriers and adjunct ingredients.

[0264] Typically the carrier for fine fragrances and perfumes is ethanolor ethanol/water. In addition to the photo-labile conjugates of thepresent invention, other pro-fragrances, pro-accords, and the like canbe included, especially species which take advantage of the differentialpH of skin. For example, acid labile pro-fragrances include orthoesters,acetals, ketals, and the like. Therefore, the combination of aphoto-labile pro-fragrance and an acid labile pro-fragrance whichreleases the same fragrance raw material, inter alia, damascone,citronellal, is one aspect encompassed by the present invention.

[0265] For the purposes of the present invention the terms “perfume” and“fine fragrance” are essentially synonymous and are used collectively orinterchangeably throughout the present specification and are taken tomean the more concentrated forms of fragrance-containing compositions.Aspects of the present invention which apply to “perfumes” willtherefore apply equally to “fine fragrances” and vice versa. Typically,colognes, eau de toilettes, after shaves, and other fragrance-containingembodiments are perfumes or fine fragrances which have a greater degreeof dilution, usually by a volatile carrier such as ethanol.

Embodiments

[0266] The following are additional non-limiting embodiments of thepresent invention.

[0267] Skin Conditioning Lotions

[0268] An example of a skin care composition of the present inventioncomprises an ester having a total number of carbon atoms in excess ofabout 28, for example lauryl laurate, lauryl myristate, myristylmyristate, behenyl caprate, cetearyl palmitate, behenyl stearate, morepreferably cetearyl palmitate and cetyl stearate.

[0269] The present compositions in addition to the esters describedherein above, contain an emollient material in an amount such that theamount of ester plus emollient is from about 0.2%, preferably from about4% to about 25%, preferably to about 18% of the total composition. Onefunction of the emollient is to ensure that the ester is plasticizedsufficiently to allow it to be in a film-like state on the skin. Theemollient in the present compositions is selected from the groupconsisting of fatty alcohols, esters having fewer than about 24 totalcarbon atoms (e.g. isopropyl palmitate), branched chain esters havinggreater than about 24 total carbon atoms (e.g. cetearyl octonate),squalane, liquid or solid paraffins, mixtures of fatty acids andsqualane, mixtures of fatty acids and liquid or solid paraffins andmixtures thereof. The aforementioned esters, those having fewer than 24carbon atoms or branched and having more than 24 carbon atoms, if usedas an emollient should preferably be used in an mount equal to about athird of the long chain ester. The particular emollient selected dependsin part on the particular ester selected since proper plasticization, asindicated above, is desired. The emollient for the esters having morethan 28 carbon atoms is preferably selected from the group consisting ofsqualane, liquid or solid paraffins and mixtures of fatty alcohols withsqualane or paraffins. Typical fatty alcohols and fatty acids useful inthe present compositions include those having from 12-22 carbon atomssuch as cetyl alcohol, myristyl alcohol, stearyl alcohol, stearic acidand palmitic acid. Paraffins include, for example, mineral oil,petrolatum and paraffin wax. It is preferred that distilled water beused in the present compositions.

[0270] Optional Components

[0271] Oil Phase Components

[0272] In addition to the long chain esters, emollients and emulsifiersdescribed previously, the oil phase of the present compositions maycontain a variety of materials including:

[0273] (a) Esters not meeting the requirements for the long chain esterand not present as an emollient, supra, such as oleyl oleate, isostearylisostearate, isopropyl lanolate, isopropyl myristate, butyl stearate,myristyl lactate and 2-ethyl hexyl palmitate;

[0274] (b) Oils such as castor oil, jojoba oil, cottonseed oil, peanutoil and sesame

[0275] (c) Waxes such as ceresin wax, carnuba wax, beeswax and castorwax;

[0276] (d) Lanolin, its derivatives and components such as acetylatedlanolin, lanolin alcohols and lanolin fatty acids. Lanolin fatty acidsare described in U.S. Pat. No. Re. 29,814, Oct. 24, 1978 to W. E. Snyderincorporated herein by reference.

[0277] (e) Polyalkylenes such as hydrogenated polyisobutene andpolyethylene; and

[0278] (f) Sterols such as cholesterol and phytosterol.

[0279] These optional oil phase materials may comprise up to about 80%of the oil phase, preferably up to about 35%. When used at these levels,the optional components do not impair the occlusive nature of thecompositions and add to the composition's total cosmetic performance.

[0280] Water Phase Components

[0281] The water phase of the compositions may contain many differentmaterials including:

[0282] (a) Humectants, such as sorbitol, glycerine, propylene glycol,alkoxylated glucose and hexanetriol at a level of from about 1% to about20%.

[0283] (b) Thickening agents such as carboxyvinyl polymers, ethylcellulose, polyvinyl alcohol, carboxymethyl cellulose, vegetable gumsand clays such as Veegum.RTM. (magnesium aluminum silicate, R. T.Vanderbilt, Inc.) at a level of from about 0.01% to about 6%;

[0284] (c) Proteins and polypeptides at a level of from about 0.1% toabout 3%;

[0285] (d) Preservatives such as the methyl, ethyl, propyl and butylesters of hydroxybenzoic acid (Parabens-Mallinckrodt ChemicalCorporation) EDTA and imidazolidinyl urea (Germall 115-SuttonLaboratories) at a level of from about 0.2% to about 2.5%; and

[0286] (e) An alkaline agent such as sodium hydroxide to neutralize, ifdesired, part of the fatty acids or thickener which may be present. Allof the percentages of these additional water phase components are of thetotal composition.

[0287] The present compositions may also contain agents suitable foraesthetic purposes such as dyes. The compositions of the presentinvention are preferably substantially free of materials that adverselyaffect their performance. Therefore, such things as polyethylene glycolsare preferably present only at levels below about 1% of the totalcomposition. The pH of the present compositions is preferably in therange of about 7.5-10.

Method of Manufacture

[0288] The compositions which comprise the skin lotion embodiments ofthe present invention generally have a lotion consistency and may be inthe form of oil-in-water or water-in-oil emulsions with the former beingpreferred because of their more pleasing cosmetic properties. Thecompositions of the present invention are preferably made by the methodcomprising the steps of;

[0289] a) preparing the oil phase;

[0290] b) preparing the water phase; and

[0291] c) adding the oil phase to the water phase.

[0292] Step (a) is carried out by heating the oil phase materials to atemperature of about 75° C. to about 100° C.. Step (b) is carried out byheating the water phase materials to a temperature about the same asthat of the oil phase. The emulsion is formed by slowly adding the oilphase prepared in step (a) to the water phase prepared in step (b) withstirring. The pro-accords which comprise the fragrance delivery systemor other ingredients may be added to the phase in which they are solubleprior to the mixing of the two phases or added directly to the mixedwater and oil phases.

[0293] In addition to the fragrance-containing compositions for use onhuman skin, the pro-accords of the present invention are also suitablefor use in any odor controlling or fragrance mediating application. Anexample of this odor control capacity is animal litter and odor controlarticles useful in lining the cages, stalls, and other living areas ofdomesticated animals. For example, U.S. Pat. No. 5,339,769 Toth et al.,issued Aug. 23, 1994 describes a process for making an absorbentcomposition, which can well accommodate the pro-accord materials of thepresent invention.

[0294] An example of a suitable litter material which comprises thephoto-labile pro-fragrance conjugates of the present invention can beformed by the following process.

[0295] A Glatt fluid bed granulator is charged with 1,0000 g ofbentonite clay (90% of the particles being greater than 420 microns) and10 g of a cellulose ether (Methocel™ K15M Premium, a cellulose etherhaving a viscosity of 15,000 centipoise (cps) as a 2% aqueous solution).The granulator is started and the product temperature is brought up toabout 40° C.(outlet temperature). When the outlet temperature reachesabout 40° C., atomized water is sprayed onto the moving powders withinthe granulator, During the granulation process, inlet air temperature ismaintained at 70° C. to 80° C.; air atomization pressure is 28-35 psi;and the spraying cycle is for 45 seconds with a 15 second shaking time.

[0296] The clay/cellulose ether agglomerates swell over time. The waterhydrates the cellulose ether polymer, which produces adhesion to formthe granule. At this time it is more advantageous to introduce thepro-accord materials and other aesthetic fragrances. The formation ofthe granule promotes aggregation of the small sized particles of theinert substrate, e.g. clay particles of about 50 to 600 microns. Theformation of a granule significantly reduces the quality of dust in thefinal product while the litter forms an agglomerate when wetted.

[0297] In an alternative embodiment of the clay-based litter boxarticles/pro-accord admixture, once the clay particles have been formed,a concentrated solution, or a carrier alcohol-based admixture of thepro-accords may be delivered to the surface of the granule by a suitablemeans.

[0298] A deodorant gel stick of the present invention having thecomposition given below, and being essentially free of water, isprepared as follows. TABLE I weight % Ingredients 5 6 7 8 Dipropyleneglycol 39.85 51.95 75.10 71.15 Sodium Stearate  5.50  5.50  5.50  5.55PPG-3 myristyl ether 29.40 25.33 15.00 19.30 Cyclomethicone-D5 21.0013.33 — — Ethanol (absolute; 200 proof)  1.80  1.44  1.95  1.50 Zincpyrithione¹  0.05  0.05  0.05  0.10 Conjugate²  2.40  0.55 0.1  0.001

[0299] All of the above materials, except the fragrance pro-accord, arevigorously mixed and heated to about 121° C. until the mixture is clear.The mixture is then cooled to about 80° C. and the pro-accord is addedwith stirring. The mixture is poured into stick molds and cooled to roomtemperature forming the deodorant gel stick compositions of the presentinvention.

[0300] A personnel cleanser composition is prepared by combining thefollowing ingredients using conventional mixing techniques. TABLE IIweight % Ingredients 9 10 11 12 Phase A Water QS 100 QS 100 QS 100 QS100 Disodium EDTA 0.100 0.100 0.100 0.100 Glycerin 4.00  4.00  4.00 4.00  Methylparaben 0.200 0.200 0.200 0.200 C₁₀-C₃₀ alkyl 0.150 0.1500.150 0.150 acrylate crosspolymer¹ Carbomer 954² 0.250 0.250 0.250 0.250Water QS 100 QS 100 QS 100 QS 100 Phase B Stearic Acid 0.110 0.110 0.1100.110 Stearyl alcohol 0.875 0.875 0.875 0.875 Cetyl alcohol 0.875 0.8750.875 0.875 Propylparaben 0.150 0.150 0.150 0.150 Steareth-2 — 0.25 0.25  0.25  Steareth-21 — 0.50  0.50  0.50  Phase C Sodium hydroxide³0.130 0.130 0.130 0.130 Phase D Diisopropyl sebacate 1.50  1.50  1.50 1.50  Isohexadecane 5.00  2.00  5.00  5.00  Mineral Oil⁴ — 5.00  — —Phase E Phenoxyethanol 0.5  0.5  — 0.5  Conjugate⁵ 1.5  1.5  — —Conjugate⁶ — — 2.20  1.5  Phase F Glucose amide 0.96  0.96  0.96  0.96 Minors, aesthetics, carriers balance balance balance balance

[0301] The above Examples 8-11 can be suitably prepared as follows. In asuitable vessel, the Phase A ingredients are mixed at room temperatureto form a dispersion and heated with stirring to 70-80° C. In a separatevessel, the Phase B ingredients are heated with stirring to 70-80° C.Phase B is then added to Phase A with mixing to form the emulsion. Next,Phase C is added to neutralize the composition. The Phase D ingredientsare added with mixing, followed by cooling to 45-50° C. The Phase Eingredients are then added with stirring, followed by cooling to 40° C.Phase F is heated with mixing to 40° C. and added to the emulsion, whichis cooled to room temperature. The resulting cleansing composition isuseful for cleansing the skin. The emulsion de-emulsifies upon contactwith the skin.

[0302] The present invention further relates to the use of photo-labilepro-fragrances in embodiments which do not contact human skin, interalia, laundry detergent compositions, hard surface cleaningcompositions, carpet cleaning compositions, and the like.

Surfactant System

[0303] The laundry detergent compositions of the present inventioncomprise a surfactant system. The surfactant systems of the presentinvention may comprise any type of detersive surfactant, non-limitingexamples of which include one or more mid-chain branched alkyl sulfatesurfactants, one or more mid-chain branched alkyl alkoxy sulfatesurfactants, one or more mid-chain branched aryl sulfonate surfactants,one or more non mid-chain branched sulphonates, sulphates, cationicsurfactants, zwitterionic surfactants, ampholytic surfactants, andmixtures thereof.

[0304] The total amount of surfactant present in the compositions of thepresent invention is from about 10% by weight, in one embodiment of thepresent invention the range of surfactant is from about 10% to about 80%by weight, of said composition. Another embodiment the amount ofsurfactant is from about 10% to about 60%, wherein another embodimentcomprises from about 15% to about 30% by weight, of said composition.

[0305] Nonlimiting examples of surfactants useful herein include:

[0306] a) C₁₁-C₁₈ alkyl benzene sulfonates (LAS);

[0307] b) C₆-C₁₈ mid-chain branched aryl sulfonates (BLAS);

[0308] c) C₁₀-C₂₀ primary, α or ω-branched, and random alkyl sulfates(AS);

[0309] d) C₁₄-C₂₀ mid-chain branched alkyl sulfates (BAS);

[0310] e) C₁₀-C₁₈ secondary (2,3) alkyl sulfates as described in U.S.Pat. No. 3,234,258 Morris, issued Feb. 8,1966; U.S. Pat. No. 5,075,041Lutz, issued Dec. 24, 1991; U.S. Pat. No. 5,349,101 Lutz et al., issuedSep. 20, 1994; and U.S. Pat. No. 5,389,277 Prieto, issued Feb. 14, 1995each incorporated herein by reference;

[0311] f) C₁₀-C₁₈ alkyl alkoxy sulfates (AE_(x)S) wherein preferably xis from 1-7;

[0312] g) C₁₄-C₂₀ mid-chain branched alkyl alkoxy sulfates (BAE_(x)S);

[0313] h) C₁₀-C₁₈ alkyl alkoxy carboxylates preferably comprising 1-5ethoxy units;

[0314] i) C₁₂-C₁₈ alkyl ethoxylates, C₆-C₁₂ alkyl phenol alkoxylateswherein the alkoxylate units are a mixture of ethyleneoxy andpropyleneoxy units, C₁₂-C₁₈ alcohol and C₆-C₁₂ alkyl phenol condensateswith ethylene oxide/propylene oxide block polymers inter alia Pluronic®ex BASF which are disclosed in U.S. Pat. No. 3,929,678 Laughlin et al.,issued Dec. 30, 1975, incorporated herein by reference;

[0315] j) C₁₄-C₂₂ mid-chain branched alkyl alkoxylates, BAE_(x);

[0316] k) Alkylpolysaccharides as disclosed in U.S. Pat. No. 4,565,647Llenado, issued Jan. 26, 1986, incorporated herein by reference;

[0317] l) Pseudoquat surfactants having the formula:

[0318] wherein R is C₄-C₁₀ alkyl, R¹ is selected from the groupconsisting of C₁-C₄ alkyl, —(CH₂CHR²O)_(y)H, and mixtures thereof; R² ishydrogen, ethyl, methyl, and mixtures thereof; y is from 1 to 5; x isfrom 2 to 4; for the purposes of the present invention, a particularlyuseful pseudoquat surfactant comprises R equal to an admixture of C₈-C₁₀alkyl, R¹ is equal to methyl; and x equal to 3; these surfactants aredescribed in U.S. Pat. No. 5.916,862 Morelli et al., issued Jun. 29,1999 included herein by reference;

[0319] m) Polyhydroxy fatty acid amides having the formula:

[0320] wherein R⁷ is C₅-C₃₁ alkyl; R⁸ is selected from the groupconsisting of hydrogen, C₁-C₄ alkyl, C₁-C₄ hydroxyalkyl, Q is apolyhydroxyalkyl moiety having a linear alkyl chain with at least 3hydroxyls directly connected to the chain, or an alkoxylated derivativethereof; preferred alkoxy is ethoxy or propoxy, and mixtures thereof.These surfactants are described in U.S. Pat. No. 5,489,393 Connor etal., issued Feb. 6, 1996; and U.S. Pat. No. 5,45,982 Murch et al.,issued Oct. 3, 1995, both incorporated herein by reference.

[0321] The mid-chain branched alkyl sulfate surfactants of the presentinvention have the formula:

[0322] the alkyl alkoxy sulfates have the formula:

[0323] the alkyl alkoxylates have the formula:

[0324] wherein R, R¹, and R² are each independently hydrogen, C₁-C₃alkyl, and mixtures thereof; provided at least one of R, R¹, and R² isnot hydrogen; preferably R, R¹, and R² are methyl; preferably one of R,R¹, and R² is methyl and the other units are hydrogen. The total numberof carbon atoms in the mid-chain branched alkyl sulfate and alkyl alkoxysulfate surfactants is from 14 to 20; the index w is an integer from 0to 13; x is an integer from 0 to 13; y is an integer from 0 to 13; z isan integer of at least 1; provided w +x +y +z is from 8 to 14 and thetotal number of carbon atoms in a surfactant is from 14 to 20; R³ isC₁-C₄ linear or branched alkylene, preferably ethylene, 1,2-propylene,1,3-propylene, 1,2-butylene, 1,4-butylene, and mixtures thereof.

[0325] M denotes a cation, preferably hydrogen, a water soluble cation,and mixtures thereof. Non-limiting examples of water soluble cationsinclude sodium, potassium, lithium, ammonium, alkyl ammonium, andmixtures thereof.

Adjunct Ingredients

[0326] The following are non-limiting examples of adjunct ingredientsuseful in the laundry compositions of the present invention, saidadjunct ingredients include builders, optical brighteners, soil releasepolymers, dye transfer agents, dispersents, enzymes, suds suppressers,dyes, perfumes, colorants, filler salts, hydrotropes, photoactivators,fluorescers, fabric conditioners, hydrolyzable surfactants,preservatives, anti-oxidants, chelants, stabilizers, anti-shrinkageagents, anti-wrinkle agents, germicides, fungicides, anti corrosionagents, and mixtures thereof.

[0327] The following are non-limiting examples of laundry detergentcompositions according to the present invention. TABLE III weight %Ingredients 13 14 15 16 Polyhydroxy coco-fatty acid amide 2.50 4.00 4.50— NEODOL 24-7¹ — 4.50 — — NEODOL 23-9² 0.63 — 4.50 2.00 C₁₅ Alkylethoxylate sulphate 20.15  4.00 5.50 20.50  C₂₅ Alkyl sulfate — 14.00 15.00  — C_(11.8) linear alkylbenzene sulfonate — — — 6.00 C₈-C₁₀Amidopropyl Amine — 1.30 — — C₁₀ Amidopropyl Amine 0.50 — — 1.50 Citricacid 3.00 2.00 3.00 2.50 C₁₂-C₁₈ fatty acid 2.00 6.50 5.00 5.00 Rapeseedfatty acid — 4.10 — 6.50 Ethanol 3.36 1.53 5.60 0.50 Propanediol 7.409.20 6.22 4.00 Monoethanolamine 1.00 7.90 8.68 0.50 Sodium hydroxide2.75 1.30 0.75 4.40 Sodium p-toluene sulfonate 2.25 — 1.90 — Borax/Boricacid 2.50 2.00 3.50 2.50 Protease³ 0.88 0.74 1.50 0.88 Lipolase⁴ — 0.120.18 — Duramyl⁵ 0.15 0.11 — 0.15 CAREZYME  0.053  0.028  0.080  0.053Dispersant⁶ 0.60 0.70 1.50 0.60 Ethoxylated polyalkyleneimine⁷ 1.20 0.701.50 1.20 Optical Brightener 0.13 0.15 0.30 0.15 Conjugate⁸ 1.0  1.5 0.2  0.02 Pro-perfume⁹ 0.01 —  0.005 — Suds suppresser 0.12 0.28 0.120.12 Minors, aesthetics, stabilizers, balance balance balance balancewater

[0328] As a non-limiting example, granular compositions are generallymade by combining base granule ingredients, e.g., surfactants, builders,water, etc., as a slurry, and spray drying the resulting slurry to a lowlevel of residual moisture (5-12%). The remaining dry ingredients, e.g.,granules of the polyalkyleneimine dispersant, can be admixed in granularpowder form with the spray dried granules in a rotary mixing drum. Theliquid ingredients, e.g., solutions of the polyalkyleneimine dispersant,enzymes, binders and perfumes, can be sprayed onto the resultinggranules to form the finished detergent composition. Granularcompositions according to the present invention can also be in “compactform”, i.e. they may have a relatively higher density than conventionalgranular detergents, i.e. from 550 to 950 g/l. In such case, thegranular detergent compositions according to the present invention willcontain a lower amount of “inorganic filler salt”, compared toconventional granular detergents; typical filler salts are alkalineearth metal salts of sulphates and chlorides, typically sodium sulphate;“compact” detergents typically comprise not more than 10% filler salt.

[0329] Liquid detergent compositions can be prepared by admixing theessential and optional ingredients thereof in any desired order toprovide compositions containing components in the requisiteconcentrations. Liquid compositions according to the present inventioncan also be in “compact form”, in such case, the liquid detergentcompositions according to the present invention will contain a loweramount of water, compared to conventional liquid detergents. Addition ofthe polyalkyleneimine dispersant to liquid detergent or other aqueouscompositions of this invention may be accomplished by simply mixing intothe liquid solutions the polyalkyleneimine dispersant.

[0330] The compositions of the present invention can be suitablyprepared by any process chosen by the formulator, non-limiting examplesof which are described in U.S. Pat. No. 5,691,297 Nassano et al., issuedNov. 11, 1997; U.S. Pat. No. 5,574,005 Welch et al., issued Nov. 12,1996; U.S. Pat. No. 5,569,645 Dinniwell et al., issued Oct. 29, 1996;U.S. Pat. No. 5,565,422 Del Greco et al., issued Oct. 15, 1996; U.S.Pat. No. 5,516,448 Capeci et al., issued May 14, 1996; U.S. Pat. No.5,489,392 Capeci et al., issued Feb. 6, 1996; U.S. Pat. No. 5,486,303Capeci et al., issued Jan. 23, 1996 all of which are incorporated hereinby reference.

[0331] The following are non-limiting examples of malodor abatementcompositions utilizing the photo-labile conjugates of the presentinvention. TABLE IV weight % Ingredients 17 18 19 20 α-Cyclodextrin 0.50— 0.50 — Hydroxy α-cyclodextrin — 1.00 — — Methylated β-cyclodextrin — —0.50 — Hydroxypropyl α-cyclodextrin — — — 0.27 Hydroxypropylβ-cyclodextrin 1.00 2.50 — 0.73 γ-Cyclodextrin 0.50 1.00 — —Anti-microbial¹  0.001 —  0.0008  0.008 Zinc chloride — — 1.0  1.0 Glutaraldehyde — 0.01 — — Ethanol — 2.00 — — Propylene glycol — — — 0.06Conjugate² 1.5  0.2  0.01  0.002 Distilled water balance balance balancebalance

[0332] The above compositions 16-19 can be prepared or used according toany of U.S. Pat. No. 5,534,165 Pilosof et al., issued Jul. 9, 1996; U.S.Pat. No. 5,593,670 Trinh et al., issued Jan. 14, 1997; U.S. Pat. No.5,686,097 Trinh et al., issued Sep. 16, 1997; U.S. Pat. No. 5,714,137Trinh et al. issued Feb. 3, 1998; U.S. Pat. No. 5,939,060 Trinh et al.,issued Aug. 17, 1999; U.S. Pat. No. 6,146,621 Trinh et al., issued Nov.14, 2000; all of which are included herein by reference.

[0333] The following is a fine fragrance accord suitable for use in afine fragrance or perfume which comprises a photo-labile conjugateaccording to the present invention. TABLE V Weight % Ingredients 21 2223 24 Pro-fragrance component Pro-fragrance¹ 1.0 — — — Pro-fragrance²2.0 — — — Pro-fragrance³ 2.0 — — — Pro-fragrance⁴ 2.0 — — —Pro-fragrance⁵ 0.9 — — — Free fragrance component Damascone 0.0001 — —0.001 Melonal 0.05 — — 0.002 Triplal 0.01 — — 0.002 Undecavertol — — —0.001 Geraniol — — — 0.004 Additional free fragrance raw 13.8 15.2 17.015.1 materials⁶ Photo-labile pro-fragrance conjugate componentConjugate⁷ 2.0 0.4 0.01 0.2 Conjugate⁸ — 0.4 0.02 0.08 Conjugate⁹ — 0.40.03 0.08 Carrier¹⁰ balance balance balance balance ¹Pro-fragranceaccording to U.S. Pat. No. 6,013,618 Morelli et al., issued January 11,2000, U.S. Pat. No. 6,077,821 Morelli et al., issued June 20, 2000 orU.S. Pat. No. 6,087,322 Morelli et al., issued July 11, 2000 whichreleases delta-damascone. ²Pro-fragrance according to U.S. Pat. No.6,013,618 Morelli et al., issued January 11, 2000, U.S. Pat. No.6,077,821 Morelli et al., issued June 20, 2000 or U.S. Pat. No.6,087,322 Morelli et al., issued July 11, 2000 which releases melonal.³Pro-fragrance according to U.S. Pat. No. 6,013,618 Morelli et al.,issued January 11, 2000, U.S. Pat. No. 6,077,821 Morelli et al., issuedJune 20, 2000 or U.S. Pat. No. 6,087,322 Morelli et al., issued July 11,2000 which releases triplal. ⁴Pro-fragrance according to U.S. Pat. No.6,013,618 Morelli et al., issued January 11, 2000, U.S. Pat. No.6,077,821 Morelli et al., issued June 20, 2000 or U.S. Pat. No.6,087,322 Morelli et al., issued July 11, 2000 which releasesundecavertol. ⁵Pro-fragrance according to U.S. Pat. No. 6,013,618Morelli et al., issued January 11, 2000, U.S. Pat. No. 6,077,821 Morelliet al., issued June 20, 2000 or U.S. Pat. No. 6,087,322 Morelli et al.,issued July 11, 2000 which releases geraniol. ⁶Conventional fragranceaccord. ⁷Photo-labile pro-fragrance conjugate according to Example 3.⁸Photo-labile pro-fragrance conjugate having the formula:

[0334] 9. Photo-labile pro-fragrance conjugate having the formula:

[0335] 10. Ethanol:water mixture (between 100:0 and 50:50).

[0336] The following are non-limiting examples of shampoo and hairconditioning compositions according to the present invention. TABLE VIweight % Ingredients 25 26 27 28 Ammonium Laureth-3 Sulfate 14.00 14.00  14.00  14.00  Cocamidopropyl betaine 2.70 2.70 2.70 2.70Polyquaternium-10 0.15 0.15 0.15 0.30 Light mineral oil 0.30 0.15 0.050.30 Cocamide MEA 0.80 0.80 0.80 0.80 Cetyl alcohol 0.42 0.42 0.42 0.42Stearyl alcohol 0.18 0.18 0.18 0.18 Ethylene glycol distearate 1.50 1.501.50 1.50 Dimethicone 1.00 1.00 1.00 3.00 DMDM hydantoin 0.37 0.37 0.370.37 Additional free fragrances 0.35 0.45 0.60 1.0  Conjugate¹  0.0010.05 0.5  1.50 Distilled water balance balance balance balance

What is claimed is:
 1. A photo-labile pro-fragrance conjugatecomprising: a) a photo-labile unit which upon exposure toelectromagnetic radiation is capable of releasing a pro-fragrance unit;and b) a pro-fragrance unit, which when so released is either i) apro-fragrance compound capable of releasing a fragrance raw material; orii) a fragrance raw material.
 2. A compound according to claim 1 whereinsaid photo-labile pro-fragrance conjugate has the formula:

wherein R is a fragrance raw material or a unit capable of releasing afragrance raw material; each R¹ is independently hydrogen, a unit whichcan substitute for hydrogen, C₁-C₁₂ substituted or unsubstitutedhydrocarbyl unit, each R² is independently hydrogen, C₁-C₁₂ substitutedor unsubstituted hydrocarbyl unit, and mixtures thereof; X is selectedfrom the group consisting of —OH, —OC(O)R¹², —OC(O)OR¹², —NHR¹², andmixtures thereof; R¹² is H, C₁-C₁₂ substituted or unsubstituted alkyl,and mixtures thereof.
 3. A compound according to claim 2 wherein X is—OH.
 4. A compound according to claim 2 wherein R¹ is hydrogen.
 5. Acompound according to claim 3 wherein said conjugate has the formula:


6. A compound according to claim 3 wherein said conjugate has theformula:

wherein R² is methyl or ethyl.
 7. A compound according to claim 4wherein said conjugate has the formula:


8. A compound according to claim 2 wherein said R¹ is one or moreelectron donating groups selected from the group consisting of hydroxy,C₁-C₁₂ linear or branched alkoxy, —N(R¹²)₂, and mixtures thereof; R¹² isH, C₁-C₁₂ alkyl, and mixtures thereof.
 9. A compound according to claim8 wherein X is hydroxy.
 10. A compound according to claim 2 wherein R²are each hydrogen.
 11. A compound according to claim 2 wherein R has theformula:

wherein each R³ is independently hydrogen, substituted or unsubstitutedC₁-C₃₀ hydrocarbyl, and mixtures thereof.
 12. A compound according toclaim 11 wherein R has the formula:

wherein each R⁴ is independently selected from the group consisting of:i) hydrogen; ii) C₁-C₂₂ substituted or unsubstituted, branched orunbranched alkyl; iii) C₂-C₂₂ substituted or unsubstituted, branched orunbranched alkenyl; iv) C₂-C₂₀ substituted or unsubstituted, branched orunbranched hydroxyalkyl; v) C₇-C₂₀ substituted or unsubstitutedalkylenearyl; vi) C₃-C₂₀ substituted or unsubstituted cycloalkyl; vii)C₆-C₂₀ aryl; viii) C₅-C₂₀ heteroaryl units comprising one or moreheteroatoms selected from the group consisting of nitrogen, oxygen,sulfur, and mixtures thereof; ix) two R⁴ units can be taken together toform one or more aromatic or non-aromatic, heterocyclic ornon-heterocyclic, single rings, fused rings, bicyclo rings,spiroannulated rings, or mixtures thereof, said rings comprising from 3to 20 carbon atoms and one or more heteroatoms selected from the groupconsisting of nitrogen, oxygen, sulfur, and mixtures thereof; x) andmixtures thereof; G¹ and G² are each independently hydrogen, C₁-C₂₀linear or branched hydrocarbyl, —Y, —C(O)Y, and mixtures thereof; Y isC₆-C₁₀ substituted or unsubstituted cyclic alkyl.
 13. A compoundaccording to claim 12 wherein Y is selected from the group consisting of2,6,6-trimethylcyclohex-2-enyl, 2,6,6-trimethylcyclohex-1-enyl,2,6,6-trimethylcyclohex-l-enyl, 2,6,6-trimethylcyclohex-3-enyl, andmixtures thereof.
 14. A compound according to claim 11 wherein R has theformula:

wherein G¹ and G² are each independently —CH₃, —C(O)CH₃, —Y, —C(O)Y, andmixtures thereof; Y is selected from the group consisting of: i)2,6,6-trimethylcyclohex-2-enyl having the formula:

ii) 2,6,6-trimethylcyclohex-1-enyl having the formula:

iii) 2,6,6-trimethylcyclohex-1-enyl having the formula:

iv) 2,6,6-trimethylcyclohex-3-enyl having the formula:

v) and mixtures thereof.
 15. A compound according to claim 11 having theformula:

wherein R¹ is hydrogen, hydroxyl, and mixtures thereof.
 16. A compoundaccording to claim 15 having the formula:


17. A compound according to claim 2 wherein R has the formula:

wherein Z is oxygen or sulfur; m is from 1 to 3; R⁵ units are selectedfrom: a) C₆-C₂₂ substituted or unsubstituted linear alkyl b) C₆-C₂₂substituted or unsubstituted branched alkyl; c) C₆-C₂₂ substituted orunsubstituted linear alkenyl; d) C₆-C₂₂ substituted or unsubstitutedbranched alkenyl; e) C₆-C₂₂ substituted or unsubstituted cycloalkyl; f)C₆-C₂₂ substituted or unsubstituted branched cycloalkyl; g) C₆-C₂₂substituted or unsubstituted cycloalkenyl; h) C₆-C₂₂ substituted orunsubstituted branched cycloalkenyl; i) C₆-C₂₂ substituted orunsubstituted aryl; j) C₆-C₂₂ substituted or unsubstitutedheterocyclicalkyl; k) C₆-C₂₂ substituted or unsubstitutedheterocyclicalkenyl; l) and mixtures thereof; R⁶ units comprise hydrogenor R⁵; R⁷ is independently selected from the group consisting of: a) R⁶;b) hydroxyl; c) a carbonyl comprising unit having the formula:—(CH₂)_(x)COR⁸ wherein R⁸ is: i) —OH; ii) —OR⁹ wherein R⁹ is hydrogen,C₁-C₁₅ substituted linear alkyl, C₁₁-C₁5 unsubstituted linear alkyl,C₁-C₁₅ substituted branched alkyl, C₁₁-C₁₅ unsubstituted branched alkyl,C₂-C₂₂ substituted or unsubstituted linear alkenyl, C₃-C₂₂ substitutedor unsubstituted branched alkenyl, or mixtures thereof, iii) —N(R¹⁰)₂wherein R¹⁰ is hydrogen, C₁-C₆ substituted or unsubstituted linearalkyl, C₃-C₆ substituted or unsubstituted branched alkyl, or mixturesthereof; iv) C₁-C₂₂ substituted or unsubstituted linear alkyl; v) C₁-C₂₂substituted or unsubstituted branched alkyl; vi) C₂-C₂₂ substituted orunsubstituted linear alkenyl; vii) C₃-C₂₂ substituted or unsubstitutedbranched alkenyl; viii) C₃-C₂₂ substituted or unsubstituted cycloalkyl;ix) C₆-C₂₂ substituted or unsubstituted aryl; x) C₆-C₂₂ substituted orunsubstituted heterocyclicalkyl; xi) C₆-C₂₂ substituted or unsubstitutedheterocyclicalkenyl; the index x is from 0 to 22; d) alkyleneoxy unitshaving the formula: —[C(R¹¹)₂]_(y)[C(R¹¹)₂C(R¹¹)₂O]_(z)R¹¹ wherein eachR¹¹ is independently; i) hydrogen; ii) —OH; iii) C₁-C₄ alkyl; iv) ormixtures thereof; two R¹¹ units can be taken together to form a C₃-C₆spiroannulated ring, carbonyl unit, or mixtures thereof; y has the valuefrom 0 to 10, z has the value from 1 to 50; e) and mixtures thereof; anytwo R⁷ units can be taken together to form: i) a carbonyl moiety; ii) aC₃-C₆ spiroannulated ring; iii) a heterocyclic aromatic ring comprisingfrom 5 to 7 atoms; iv) a non-heterocyclic aromatic ring comprising from5 to 7 atoms; v) a heterocyclic ring comprising from 5 to 7 atoms; vi) anon-heterocyclic ring comprising from 5 to 7 atoms; vii) or mixturesthereof.
 18. A compound according to claim 17 wherein R has the formula:

wherein R⁶ is selected from the group consisting of hydrogen and methyl.19. A compound according to claim 17 wherein R has the formula:

wherein R⁶ is selected from the group consisting of hydrogen and methyl;each R⁷ is independently hydrogen, methyl or —C(O)OR⁹, and mixturesthereof; R⁹ is hydrogen, C₁-C₁₂ alkyl, and mixtures thereof.
 20. Acomposition according to claim 17 having the formula:


21. A composition according to claim 17 having the formula:


22. A compound according to claim 11 having the formula:

wherein R′ is derived from an alcohol having the formula R′OH.
 23. Aphoto-labile pro-fragrance conjugate having the formula: [photo-labileunit]—(L)n—[pro-fragrance unit] wherein said [photo-labile unit] isselected from the group consisting of:

wherein each R¹ is independently hydrogen, a unit which can substitutefor hydrogen, C₁-C₁₂ substituted or unsubstituted hydrocarbyl unit; saidunits which can substitute for hydrogen are selected from the groupconsisting of; i) —NHCOR³⁰; ii) —COR³⁰; iii) —COOR³⁰; iv) —COCH=CH₂; v)—C(=NH)NH₂; vi) —N(R³⁰)₂; vii) —NHC₆H₅; viii) =CHC₆H₅; ix) —CON(R ³⁰)₂;x) —CONHNH₂; xi) —NHCN; xii) —OCN; xiii) —CN; xiv) F, Cl, Br, l, andmixtures thereof; xv) =O; xvi) —OR³⁰; xvii) —NHCHO; xviii) —OH; xix)—NHN(R³ )₂; xx) =NR³⁰; xxi) =NOR³⁰; xxii) —NHOR³⁰; xxiii) —CNO; xxiv)—NCS; xxv) =C(R³⁰ )₂; xxvi) —SO₃M; xxvii) —OSO₃M; xxviii) —SCN; xxix)—P(O)H₂; xxx) —PO₂; xxxi) —P(O)(OH)₂; xxxii) —SO₂NH₂; xxxiii) —S0₂R³⁰;xxxiv) —NO₂; xxxv) —CF₃, —CCl₃, —CBr₃; xxxvi) and mixtures thereof;wherein R³⁰ is hydrogen, C₁-C₂₀ linear or branched alkyl, C₆-C₂₀ aryl,C₇-C₂₀ alkylenearyl, and mixtures thereof; M is hydrogen, or a saltforming cation; each R² is independently hydrogen, C₁-C₁₂ alkyl, andmixtures thereof; X is selected from the group consisting of —OH,—NHR¹², and mixtures thereof; R¹² is H, C₁-C₁₂ alkyl, and mixturesthereof; B is selected from the group consisting of:

L units are —OC(O)—, —NR³C(O)—, —OC(R³R⁴)—, —C(O)—, and mixturesthereof; n is 0 or 1; the [pro-fragrance unit] has the formula:

wherein each R³ is independently hydrogen, substituted or unsubstitutedC₁-C₃₀ hydrocarbyl, and mixtures thereof.
 24. A compound according toclaim 23 wherein said [photo-labile unit] has the formula:

wherein R¹ is hydrogen, hydroxyl, and mixtures thereof.
 25. A compoundaccording to claim 23 wherein said [pro-fragrance unit] has the formula:

wherein each R⁴ is independently selected from the group consisting of:i) hydrogen; ii) C₁-C₂₂ substituted or unsubstituted, branched orunbranched alkyl; iii) C₂-C₂₂ substituted or unsubstituted, branched orunbranched alkenyl; iv) C₂-C₂₀ substituted or unsubstituted, branched orunbranched hydroxyalkyl; v) C₇-C₂₀ substituted or unsubstitutedalkylenearyl; vi) C₃-C₂₀ substituted or unsubstituted cycloalkyl; vii)C₆-C₂₀ aryl; viii) C₅-C₂₀ heteroaryl units comprising one or moreheteroatoms selected from the group consisting of nitrogen, oxygen,sulfur, and mixtures thereof; ix) two R⁴ units can be taken together toform one or more aromatic or non-aromatic, heterocyclic ornon-heterocyclic, single rings, fused rings, bicyclo rings,spiroannulated rings, or mixtures thereof, said rings comprising from 3to 20 carbon atoms and one or more heteroatoms selected from the groupconsisting of nitrogen, oxygen, sulfur, and mixtures thereof; x) andmixtures thereof; G¹ and G² are each independently hydrogen, C₁-C₂₀linear or branched hydrocarbyl, —Y, —C(O)Y, and mixtures thereof; Y isC₆-C₁₀ substituted or unsubstituted cyclic alkyl.
 26. A compoundaccording to claim 25 wherein Y is selected from the group consisting of2,6,6-trimethylcyclohex-2-enyl, 2,6,6-trimethylcyclohex- 1-enyl,2,6,6-trimethylcyclohex- 1-enyl, 2,6,6-trimethylcyclohex-3-enyl, andmixtures thereof.
 27. A compound according to claim 23 wherein said[pro-fragrance unit] has the formula:

wherein G¹ and G² are each independently —CH₃, —C(O)CH₃, —Y, —C(O)Y, andmixtures thereof; Y is selected from the group consisting of: i)2,6,6-trimethylcyclohex-2-enyl having the formula:

ii) 2,6,6-trimethylcyclohex-1-enyl having the formula:

iii) 2,6,6-trimethylcyclohex-1-enyl having the formula:

iv) 2,6,6-trimethylcyclohex-3-enyl having the formula:

v) and mixtures thereof.
 28. A compound according to claim 23 whereinsaid [pro-fragrance unit] has the formula:

wherein Z is oxygen or sulfur; m is from 1 to 3; R⁵ units are selectedfrom: a) C₆-C₂₂ substituted or unsubstituted linear alkyl b) C₆-C₂₂substituted or unsubstituted branched alkyl; c) C₆-C₂₂ substituted orunsubstituted linear alkenyl; d) C₆-C₂₂ substituted or unsubstitutedbranched alkenyl; e) C₆-C₂₂ substituted or unsubstituted cycloalkyl; f)C₆-C₂₂ substituted or unsubstituted branched cycloalkyl; g) C₆-C₂₂substituted or unsubstituted cycloalkenyl; h) C₆-C₂₂ substituted orunsubstituted branched cycloalkenyl; i) C₆-C₂₂ substituted orunsubstituted aryl; j) C₆-C₂₂ substituted or unsubstitutedheterocyclicalkyl; k) C₆-C₂₂ substituted or unsubstitutedheterocyclicalkenyl; l) and mixtures thereof; R⁶ units comprise hydrogenor R⁵; R⁷ is independently selected from the group consisting of: a) R⁶;b) hydroxyl; c) a carbonyl comprising unit having the formula:—(CH₂)_(x)COR⁸ wherein R⁸ is: i) —OH; ii) —OR⁹ wherein R⁹ is hydrogen,C₁-C₁₅ substituted linear alkyl, C₁₁-C₁₅ unsubstituted linear alkyl,C₁-C₁₅ substituted branched alkyl, C₁₁-C₁₅ unsubstituted branched alkyl,C₂-C₂₂ substituted or unsubstituted linear alkenyl, C₃-C₂₂ substitutedor unsubstituted branched alkenyl, or mixtures thereof, iii) —N(R¹⁰)₂wherein R¹⁰ is hydrogen, C₁-C₆ substituted or unsubstituted linearalkyl, C₃-C₆ substituted or unsubstituted branched alkyl, or mixturesthereof; iv) C₁-C₂₂ substituted or unsubstituted linear alkyl; v) C₁-C₂₂substituted or unsubstituted branched alkyl; vi) C₂-C₂₂ substituted orunsubstituted linear alkenyl; vii) C₃-C₂₂ substituted or unsubstitutedbranched alkenyl; viii) C₃-C₂₂ substituted or unsubstituted cycloalkyl;ix) C₆-C₂₂ substituted or unsubstituted aryl; x) C₆-C₂₂ substituted orunsubstituted heterocyclicalkyl; xi) C₆-C₂₂ substituted or unsubstitutedheterocyclicalkenyl; the index x is from 0 to 22; d) alkyleneoxy unitshaving the formula: —[C(R¹¹)₂]_(y)[C(R¹¹)₂C(R¹¹)₂O]_(z)R¹¹ wherein eachR¹¹ is independently; i) hydrogen; ii) —OH; iii) C₁-C₄ alkyl; iv) ormixtures thereof; two R¹¹ units can be taken together to form a C₃-C₆spiroannulated ring, carbonyl unit, or mixtures thereof; y has the valuefrom 0 to 10, z has the value from 1 to 50; e) and mixtures thereof; anytwo R⁷ units can be taken together to form: i) a carbonyl moiety; ii) aC₃-C₆ spiroannulated ring; iii) a heterocyclic aromatic ring comprisingfrom 5 to 7 atoms; iv) a non-heterocyclic aromatic ring comprising from5 to 7 atoms; v) a heterocyclic ring comprising from 5 to 7 atoms; vi) anon-heterocyclic ring comprising from 5 to 7 atoms; vii) or mixturesthereof.
 29. A photo-labile pro-fragrance conjugate delivery systemcomprising: A) from about 0.001% by weight, of a photo-activatedpro-fragrance conjugate, said conjugate comprising: a) a photo-labileunit which upon exposure to electromagnetic radiation is capable ofreleasing a pro-fragrance unit; b) a pro-fragrance unit, which when soreleased is either: i) a pro-fragrance compound capable of releasing afragrance raw material; or ii) a fragrance raw material; and B) thebalance carriers and adjunct ingredients.
 30. A system according toclaim 29 wherein said photo-labile pro-fragrance conjugate has theformula:

wherein R is a fragrance raw material or a unit capable of releasing afragrance raw material; each R¹ is independently hydrogen, a unit whichcan substitute for hydrogen, C₁-C₁₂ substituted or unsubstitutedhydrocarbyl unit, each R² is independently hydrogen, C₁-C₁₂ substitutedor unsubstituted hydrocarbyl unit, and mixtures thereof; X is selectedfrom the group consisting of —OH, —OC(O)R¹², —OC(O)OR¹², —NHR¹², andmixtures thereof; R¹² is H, C₁-C₁₂ substituted or unsubstituted alkyl,and mixtures thereof.
 31. A system according to claim 30 wherein R hasthe formula selected from the group consisting of:

iii) and mixtures thereof; wherein each R⁴ is independently selectedfrom the group consisting of: i) hydrogen; ii) C₁-C₂₂ substituted orunsubstituted, branched or unbranched alkyl; iii) C₂-C₂₂ substituted orunsubstituted, branched or unbranched alkenyl; iv) C₂-C₂₀ substituted orunsubstituted, branched or unbranched hydroxyalkyl; v) C₇-C₂₀substituted or unsubstituted alkylenearyl; vi) C₃-C₂₀ substituted orunsubstituted cycloalkyl; vii) C₆-C₂₀ aryl; viii) C₅-C₂₀ heteroarylunits comprising one or more heteroatoms selected from the groupconsisting of nitrogen, oxygen, sulfur, and mixtures thereof; ix) two R⁴units can be taken together to form one or more aromatic ornon-aromatic, heterocyclic or non-heterocyclic, single rings, fusedrings, bicyclo rings, spiroannulated rings, or mixtures thereof, saidrings comprising from 3 to 20 carbon atoms and one or more heteroatomsselected from the group consisting of nitrogen, oxygen, sulfur, andmixtures thereof; x) and mixtures thereof; G¹ and G² are eachindependently hydrogen, C₁-C₂₀ linear or branched hydrocarbyl, —Y,—C(O)Y, and mixtures thereof; Y is C₆-C₁₀ substituted or unsubstitutedcyclic alkyl; Z is oxygen or sulfur; m is from 1 to 3; R⁵ units areselected from: a) C₆-C₂₂ substituted or unsubstituted linear alkyl b)C₆-C₂₂ substituted or unsubstituted branched alkyl; c) C₆-C₂₂substituted or unsubstituted linear alkenyl; d) C₆-C₂₂ substituted orunsubstituted branched alkenyl; e) C₆-C₂₂ substituted or unsubstitutedcycloalkyl; f) C₆-C₂₂ substituted or unsubstituted branched cycloalkyl;g) C₆-C₂₂ substituted or unsubstituted cycloalkenyl; h) C₆-C₂₂substituted or unsubstituted branched cycloalkenyl; i) C₆-C₂₂substituted or unsubstituted aryl; j) C₆-C₂₂ substituted orunsubstituted heterocyclicalkyl; k) C₆-C₂₂ substituted or unsubstitutedheterocyclicalkenyl; l) and mixtures thereof; R⁶ units comprise hydrogenor R⁵; R⁷ is independently selected from the group consisting of: a) R⁶;b) hydroxyl; c) a carbonyl comprising unit having the formula:—(CH₂)_(x)COR⁸ wherein R⁸ is: i) —OH; ii) —OR⁹ wherein R⁹ is hydrogen,C₁-C₁₅ substituted linear alkyl, C₁₁-C₁₅ unsubstituted linear alkyl,C₁-C₁₅ substituted branched alkyl, C₁-C₁₅ unsubstituted branched alkyl,C₂-C₂₂ substituted or unsubstituted linear alkenyl, C₃-C₂₂ substitutedor unsubstituted branched alkenyl, or mixtures thereof, iii) —N(R¹⁰)₂wherein R¹⁰ is hydrogen, C₁-C₆ substituted or unsubstituted linearalkyl, C₃-C₆ substituted or unsubstituted branched alkyl, or mixturesthereof; iv) C₁-C₂₂ substituted or unsubstituted linear alkyl; v) C₁-C₂₂substituted or unsubstituted branched alkyl; vi) C₂-C₂₂ substituted orunsubstituted linear alkenyl; vii) C₃-C₂₂ substituted or unsubstitutedbranched alkenyl; viii) C₃-C₂₂ substituted or unsubstituted cycloalkyl;ix) C₆-C₂₂ substituted or unsubstituted aryl; x) C₆-C₂₂ substituted orunsubstituted heterocyclicalkyl; xi) C₆-C₂₂ substituted or unsubstitutedheterocyclicalkenyl; the index x is from 0 to 22; d) alkyleneoxy unitshaving the formula: —[C(R¹¹)₂]_(y)[C(R¹¹)₂C(R¹¹)₂O]_(z)R¹¹ wherein eachR¹¹ is independently; i) hydrogen; ii) —OH; iii) C₁-C₄ alkyl; iv) ormixtures thereof; two R¹¹ units can be taken together to form a C₃-C₆spiroannulated ring, carbonyl unit, or mixtures thereof; y has the valuefrom 0 to 10, z has the value from 1 to 50; e) and mixtures thereof; anytwo R⁷ units can be taken together to form: i) a carbonyl moiety; ii) aC₃-C₆ spiroannulated ring; iii) a heterocyclic aromatic ring comprisingfrom 5 to 7 atoms; iv) a non-heterocyclic aromatic ring comprising from5 to 7 atoms; v) a heterocyclic ring comprising from 5 to 7 atoms; vi) anon-heterocyclic ring comprising from 5 to 7 atoms; vii) or mixturesthereof.
 32. A laundry detergent comprising: A) from about 0.001% byweight, of a photo-activated pro-fragrance conjugate, said conjugatecomprising: a) a photo-labile unit which upon exposure toelectromagnetic radiation is capable of releasing a pro-fragrance unit;b) a pro-fragrance unit, which when so released is either i) apro-fragrance compound capable of releasing a fragrance raw material; orii) a fragrance raw material; B) from about 10% by weight, of adetersive surfactant; and C) the balance carriers and adjunctingredients.
 33. A perfume or fine fragrance comprising: A) from about0.001% by weight, of one or more photo-activated pro-fragranceconjugates, said conjugates each comprising: a) a photo-labile unitwhich upon exposure to electromagnetic radiation is capable of releasinga pro-fragrance unit; b) a pro-fragrance unit, which when so released iseither i) a pro-fragrance compound capable of releasing a fragrance rawmaterial; or ii) a fragrance raw material; B) from about 0.01% to about99% by weight, of an admixture of fragrance raw materials; and C) thebalance carriers and adjunct ingredients.
 34. A hair shampoo orconditioner comprising: A) from about 0.001% by weight, of one or morephoto-activated pro-fragrance conjugates, said conjugates eachcomprising: a) a photo-labile unit which upon exposure toelectromagnetic radiation is capable of releasing a pro-fragrance unit;b) a pro-fragrance unit, which when so released is either i) apro-fragrance compound capable of releasing a fragrance raw material; orii) a fragrance raw material; B) from about 0.01% to about 5% by weight,of an admixture of fragrance raw materials; and C) the balance carriersand adjunct ingredients.